DE3138301A1 - POLYFLUOROALLYL ETHER AND THEIR PRODUCTION AND USE - Google Patents

Description

Polyfluoroallyl ethers and their production and use

The present invention relates to new polyfluoroallyl ethers as well as their manufacture and use.

Various polyfluoroallyl ethers and their polymers are already known, for example in JP-OS 82713/1978 is shown.

The present invention relates to new polyfluoroallyl ethers, which are characterized in that they contain a cyano group in the molecule, as well as their polymers with other monomers copolymerizable therewith.

The polyfluoroallyl ethers of the present invention are represented by the formula

CFX = CX-CF ₂ -OC-CFY ₂ (D.

CN

representable, in which the X are the same or different and each represent a chlorine or fluorine atom and the Y are identical or different and each represent a hydrogen, Chlorine or fluorine atom.

The polyfluoroallyl ethers (I) are, in general, under colorless, stable liquids under atmospheric conditions. Specific examples are perfluoro (4-oxa-5-cyano-5-methy1-1-hexen), 4-oxa-5-cyano-5-trifluoromethyl-1-chloro-1,2,3,3,6,6,6-heptafluoro-1-hexene, 4-oxa-5-cyano-5-trifluoromethyl-2-chloro-1,1,3,3,6,6,6-heptafluoro-1-hexene, 4-Oxa-5-cyano-5-trifluoromethyl-1,2-dichloro-1,3,3,6,6,6-hexafluoro-1-hexene Etc. .

: * "'j :: <* ^: .. ^: j. 31383qi

The polyfluoroallyl ethers (I) can thereby be produced that the corresponding fluoroketone cyanohydrin salt of the formula

CFY
!

MO-C-CFY- (II)

I ^Z
CN

in which M stands for an alkali metal and the Y have the meaning given above, with a fluoropropenyl halide the formula

CFX = CX-CF ₂ -Z (III),

in which Z stands for a halogen atom other than fluorine and the X has the meaning given above, is reacted, preferably in an aprotic solvent.

The fluoroketone cyanohydrin salt (II) used as the starting material can be produced in this way, for example that the corresponding fluoroketone of the formula

CFY ₂
O = C-CFY ₂ (IV)

in which the Y are as defined above, for reaction with an alkali metal cyanide in tetrahydrofuran as reported by T. Mill et al, J.Org.Chem.

29_, 3715 (1964). It is preferred that the reaction system is anhydrous, since the solution containing the fluoroketone cyanohydrin salt (II) formed is normally used as such for the reaction with the fluoropropenyl halide (III), which is intended to be carried out under water-free conditions. On the other hand, since the fluoroketone cyanohydrin salt (II) is stable, it can also be isolated from the reaction mixture

and then for reaction with the fluoropropenyl halide (III) can be used.

As stated above, the reaction between the fluoroketone cyanohydrin salt (XI) and the fluoropropenyl halide (III) preferably carried out in an aprotic solvent. Examples of aprotic Solvents are tetrahydrofuran, dioxane, glyne, diglyme, Triglyme, dimethylformamide, dimethylacetamide, acetonitrile, suIfolane, nitrobenzene, benzonitrile, etc ».

There is no particular limitation on the reaction temperature, and usually a temperature becomes between the melting point and the boiling point of the aprotic solvent, in particular adjacent on both sides the room temperature. The reaction time is preferably no more than about 20 hours, since the longer the reaction time, the formation of a high-boiling compound as a by-product increases. It is preferred to keep the reaction system in the anhydrous state.

The polyfluoroallyl ether (I) can oligomerize with itself will. In general, however, it is polymerized with at least one ethylenically unsaturated monomer, so that a polymer is formed with a cyano group that can easily be converted into another group, for example a carboxy1 group, is transferable. In this way is the polyfluoroallyl ether "(I) as a regulator substance, in particular as a regulator substance introducing cyano groups, for polymers of value.

The polyfluoroallyl ether is used to produce modified polymers (I) together with at least one ethylenically unsaturated monomer after the polymerization subject to a procedure that is customary per se. The ethylenically unsaturated monomer can be any monomer be that with the polyfluoroallyl ether (I) copoly-

is merizable; specific examples are ethylene, propylene, vinyl chloride, vinylidene chloride, acrylic acid, Methacrylic acid, tetrafluoroethylene, trifluoroethylene, vinylidene fluoride, Vinyl fluoride, ■ hexafluoropropylene, chlorotrifluoroethylene, Perfluoro (methyl vinyl ether), perfluoro (propyl vinyl ether), etc.. Of these, fluorine-containing Monomers from the viewpoint of effectively utilizing the characteristic properties of the polyfluoroallyl ether (I) preferred, which also contains fluorine atoms.

The polymerization can be carried out by any of the conventional methods, such as bulk polymerization, solution polymerization, suspension polymerization or emulsion polymerization. In order to effectively carry out the polymerization, an inert solvent such as trichlorotrifluoroethane, dichlorotetrafluoroethane, trichlorofluoromethane, dichlorodifluoromethane, perfluorocyclobutane or water is usually used. Any substance customary for this purpose can be used as the polymerization initiator, provided it does not impair the properties of the polymer to be produced. Specific examples are di (fluoroacyl) peroxides, di (chlorofluoroacyl) peroxides, dialkyl peroxydicarbonates (e.g. diisopropyl peroxydicarbonate), diacyl peroxides (e.g. isobutyryl peroxide), peroxyesters (e.g. t-butyl peroxyisobutyrate, t-butyl peroxypivalate) etc. If desired, a chain transfer agent such as is commonly used in free radical polymerization (eg isoparaffin, tetrachldromethane, dimethyl malonate, diethyl ether, mercaptans, alcohols) can be used. The polymerization temperature is not limited and may usually be from tree temperature to 100 ⁰ C. The autogenous pressure or an increased pressure can be used as the polymerization pressure.

The polymer produced in this way can have any content ε η polyfluoroallyl ether (I) units

exhibit. From the point of view of the properties of the polymer and the economical production of one however, it is preferred for such a polymer that the content is from 0.1 to 50 mol percent.

The polymer of the invention can be brought into a suitable shape by means of a shaping process which is customary per se will. In this way, it is well suited for making molded articles. The polymer can but also because of the characteristic properties of the cyano groups contained therein as adhesives or adhesives be used. Since the cyano group is a reactive center for vulcanization, that can Polymer are heated for the purpose of crosslinking in the presence of a catalyst such as tetraphenyltin, whereby the physical properties can be changed.

The polymer can also be used for hydrolysis of the cyano group to form a carboxyl group with conc. Alkali treated. The product obtained is as an ion exchanger, can be used.

Practical and presently preferred embodiments of the present invention are illustrated in the following examples explained in more detail.

example 1

A mixture of hexafluoroacetone (hereinafter referred to as "HFA") (8.79 g) and potassium cyanide (2.51 g) in Diglyme (20 ml) was stirred for 4 d at room temperature. 3-chloropentafluoropropene was added to the reaction mixture (hereinafter referred to as "CPFP" for short) (6.68 g) was added and the mixture was stirred at room temperature for 3 hours. The reaction mixture was fractionally distilled,

* a

whereby perfluoro (4-oxa-5-cyano-5-methyl-1-hexene) was obtained; . B.p. 83-84 ⁰ C; Yield 32%.
Analysis: Calc .: C: 26.0%; N: 4.33%;

found: C: 25.3%; N: "4.17%.
IR spectrum (cm " ¹ ): 2280 (CsN), 1790 (C = C), 1300-1100 (CF),

990 (CF ₂ -OC).
Mass spectrum: 323 (M ⁺ ), 304 ((M - F) ⁺ ), 276 (a peak of a metastable ion with 323 occurred at 236),

^19th

(CF ₂ = CF-CF ₂ ⁺ ).

F-NMR spectrum:

F _r , 5

C = C-CF ₀ -OC- (CF 2,

1 I - CN

Chemical shift coupling constant

(ppm)

(Hz)

+ 7.3

+1.8-15.1

- 28.2

-114.1

Doublet J ₁₄ 1 23.6 Multiplet Triplet J ₁₂ 4.7 Doublet J ₃₄ 1 53.6 Doublet J ₃₅ 41.5 Triplet J ₃₁ 7.6 Doublet J ₄₅ 18.9 Doublet J ₄₃ 53.6 Triplet J ₄₁ 23.6 Doublet J ₅₄ 18.9 Doublet J ₅₃ 41.5 Triplet J ₅₁ 8.8

Remarks:

* 1) In comparison with trifluoroacetic acid, the Side of the lower magnetic field positive and the side of the higher magnetic field negative draws;

* 2) apparent coupling constant.

A disubstituted compound, ie (CF ₃ J ₂ (CN) COCF = CFCf ₂ OC (CN) (CF ₃ J ₂ (hereinafter referred to as the "high-boiling product"), was obtained as a by-product; yield 1.7%. -

Example 2

In the same manner as in Example 1, HFA (20.27 g) was reacted with potassium cyanide (7.21 g) at room temperature for 18 hours. To the reaction mixture was added CPFP (20.52 g) and the mixture was allowed to stand at room temperature for 1 hour touched. As a result, perfluoro (4-oxa-5-cyano-5-methyl-1-hexene) obtained in a yield of 21.8%; the high-boiling product was only produced in trace amounts.

Example · '3

The same working steps as in Example 1 were carried out carried out, but with the exception that the reaction was continued for 21 hours after the addition of the CPFP; included were perfluoro (4-oxa-5-cyano-5-methyl-1-hexene) in one Yield of 8.7% and the high-boiling product obtained in a yield of 16.6%.

Example 4

Perfluoro (4-oxa-5-cyano-5-methyl-1-hexene) (1.80 g) and tetrafluoroethylene (5.0 g) in the presence of [H ( CgF ₁₂ ) COl ₂ O ₂ as initiator and trichlorotrifluoroethane (10 ml) as solvent at 25 ^° C. for 40 h

»Ι ....— .. = :: - .. ■.;. 31383O1

- 11 -

polymerized under its own pressure. Volatile constituents were removed from the reaction mixture, whereby a perfluoro (4-oxa-5-cyano-5-methyl-1-hexene) / tetrafluoroethylene copolymer was obtained as a white solid (1.20 g); M.p. 323 ° C; IR spectrum (cm " ¹ ): 990 (CF ₂ -OC); Perfluoro (4-oxa-5-cyano-5-methyl-1-hexene) content 46 mol percent (calculated from the ratio of the IR extinctions on the Basis of CF ₉ -OC and of CF ₉ = CF ₀ ).

A sheet formed from this white solid became 18h refluxed in 5 N NaOH. The IR spectrum of the film obtained in this way showed a characteristic band

-1 -
at 1650 cm (-C00), confirming the conversion of the cyano groups to carboxy1 groups.

Example 5
15th

and_Hexaf luorop_rop_en

_{Purified water (1500 ml) and Na 2} HPO ₄ * 12 H ₃ O (7.5 g) were placed in a stainless steel autoclave having a volume of 3000 ml, and the atmosphere inside was then carefully replaced with hexafluoropropene . Thereafter, perfluoro (4-oxa-5-cyano-5-methyl-1-hexene) (10 g) was added, and a mixture of vinylidene fluoride and hexafluoropropene in a molar ratio 1: 1 was introduced with stirring at 8O ⁰ C, so that a pressure of 11.8 bar gauge reading (12 kg / cm ² G) was obtained. Immediately after adding a 5 percent. aqueous solution of ammonium persulfate (50 ml) the polymerization started. The polymerization was continued for 3.5 hours, during which time a mixture of vinylidene fluoride, hexafluoropropene and perfluoro (4-oxa-5-cyano-5-methyl-1-hexene) in a molar ratio of 78: 21: 1 was fed to the Keep pressure constant.

After 4.2 mol of the mixture had been consumed, the pressure was reduced. The resulting white aqueous dispersion was diluted with twice the volume of water, and a 1 percent strength was added with stirring. aqueous solution of potassium alum added. The precipitated substance was "collected, washed and" joLi ooknol, wodurtrh α i η Ι'ιτΠ uoro (4-OXd- ¹ J-cyano-'j-methyl-1-hexene) / vinylidene fluoride / hexafluoropropene terpolymer as a gum resin ^ was obtained (355 g) -

The intrinsic viscosity [*?] Of this rubber in tetrahydrofuran at 35 ° C was 0.72. In the IR spectrum recorded on a film produced by drawing the tetrahydrofuran solution onto a salt plate, a weak peak at 990 cm ″ was detected, which is de
(CF ₂ -OC) can be assigned.

at 990 cm ", that of the allyl ether structure

The rubber can easily be vulcanized with hexamethylene diamine carbamate. ^{When heated to 200 °} C. in the presence of tetraphenyltin, it forms a gel.

Claims (10)

Daikin Kogyo Co., Ltd. Claims Polyfluoroallyl ethers of the formula CF FX-CX-CF ₂ -OC-CFY ₂ wherein the X are identical or different and each represent a chlorine or fluorine atom and the Y are identical or are each different for a hydrogen, chlorine or Fluorine atom stand. 2. polyfluoroallyl ether according to claim 1, characterized in that that each Y stands for a fluorine atom. 3. polyfluoroallyl ether according to claim 1 or 2, characterized characterized in that each X stands for a fluorine atom. 4. polyfluoroallyl ether according to claim 1 or 2, characterized characterized in that one X stands for a fluorine atom and the other X for a chlorine atom. 5. polyfluoroallyl ether according to claim 1 or 2, characterized characterized in that each X stands for a chlorine atom. 6. Process for the preparation of polyfluoroallyl ethers of formula CFX = CX-CF ₀ -OC-CFY ₉ • I
CN wherein the X are identical or different and each represent a chlorine or fluorine atom and the Y are identical or are different and each stand for a hydrogen, chlorine or fluorine atom, characterized in that a Fluoroketone cyanohydrin salt of the formula MO-C-CFY ₂
CN in which M stands for an alkali metal and the Y have the meaning given above, with a fluoropropenyl halide the formula CFX = CX-CF ₂ -Z, in which Z stands for a halogen atom other than fluorine and the X has the meaning given above, is made to react. 7. The method according to claim 6, characterized in that the reaction is carried out in an aprotic solvent will. 8. The method according to claim 6, characterized in that the reaction at a temperature between the melting point and the boiling point of an aprotic solvent. a · η * η λ ty - .: :: * ° 'j .ι. 313 8 3 ο τ 9. Polymer containing units of a polyfluoroallyl ether the formula CFY ₀ I ² CFX = CX-CF ₂ -OC-CFY ₂
- CN wherein the X are identical or different and each represent a chlorine or fluorine atom and the Y are identical or are different and each represent a hydrogen, chlorine or fluorine atom. 10. Polymer according to claim 9, characterized in that the content of the polyfluoroallyl ether units is from 0.1 to 50 mol percent.